Alkene generation using metal sulfide particles

ABSTRACT

Systems and methods include providing a gaseous alkane input stream and metal sulfide (MSx) particles that can react with an alkane in the gaseous alkane input stream to generate an alkene, a reduced metal sulfide (MSx-1) particle, and at least one of: hydrogen sulfide (H2S) and at least one sulfur containing compound selected from: S2, CS, and CS2. A product stream can be collected that includes the alkene and at least one of: hydrogen sulfide (H2S) and the at least one sulfur containing compound. A reduced metal sulfide (MSx-1) particle reacts with sulfur in a sulfur stream and can generate the metal sulfide (MSx) particle and hydrogen (H2).

CROSS-REFERENCE TO RELATED APPLICATION(S)

The present application is a U.S. national stage entry of InternationalPatent Application No. PCT/US2020/027324, filed on Apr. 8, 2020, whichclaims priority to U.S. Provisional Patent Application No. 62/831,617,filed on Apr. 9, 2019, the entire contents of each of which are fullyincorporated herein by reference.

TECHNICAL FIELD

The present disclosure relates to systems and methods for alkenegeneration. More particularly, the present disclosure relates to systemsand methods for alkene generation using reducible metal sulfideparticles.

INTRODUCTION

Alkanes exhibit a tendency to dehydrogenate to alkenes at hightemperatures through an endothermic reaction. Industrially, this isaccomplished by the steam cracking process and is commonly used fornon-catalytic conversion of ethane to ethylene. Thermal cracking orsteam cracking relies on thermally activating the hydrocarbon feedstockto produce cracked or smaller hydrocarbons or unsaturated hydrocarbons.The cracking process takes place by gas phase radical mechanism, wherethe hydrocarbon radicals undergo initiation, propagation and terminationsteps. Typically, longer hydrocarbon chain cracking reactions to smallerhydrocarbons are preferred over unsaturated hydrocarbons. Thus, propaneor higher alkanes tend to produce ethylene instead of their respectivealkenes, and therefore require a catalyst to ensure that the desiredalkene product is the kinetically favored product.

Taking the example of propylene production, the most common andcommercially available method is propane dehydrogenation (PDH). Thebasic principle involves dehydrogenation of propane over a catalyst toform propylene and hydrogen, as shown in equation 1 below.

$\begin{matrix}{{C_{3}H_{8}}\overset{{Catalyst},\Delta}{\rightarrow}{{C_{3}H_{6}} + H_{2}}} & (1)\end{matrix}$

This reaction is performed at a lower temperature than in steam crackingreactions, catalyzing the C—H bond activation in propane with no orminimal C—C bond activation. These PDH processes typically are run ineither fixed bed reactors or fluidized bed reactors at temperaturesranging from 500-700° C. and pressures from 0.5-3 bar. Out of theseveral commercially available systems, two processes have beenhighlighted in this section. The Catofin process, by Lummus, which usesa CrO_(x) on Al₂O₃ catalyst with Na/K as promoters and the Oleflexprocess, by UOP, which uses a Pt—Sn alloy on Al₂O₃ catalyst with Na/Kpromoters. Both of these processes suffer from carbon deposition on thecatalyst, and subsequent gradual catalyst deactivation.

Reactivation of a deactivated catalyst either requires reducing thecatalyst with hydrogen, or using chlorine gas to disperse the sinteredactive sites, where the carbon is typically burnt off with airoxidation. Additionally, as seen from FIG. 1, the PDH process for allalkanes is limited by the thermodynamic equilibrium of the reaction inequation 1. Thus, in order to achieve higher propane conversions, thereaction would need to be run at a higher temperature. However, highertemperatures tend to favor C—C bond activation, reducing the selectivityand limiting the operational matrix of the process.

In order to address this trade-off, several catalytic technologies havebeen developed which introduce an oxidizing gas into the system, thuscreating a sink for hydrogen. This allows for higher conversion of thealkane in order to restore the dehydrogenation equilibrium. This processis known as oxidative dehydrogenation (ODH) and is widely used forethane and propane dehydrogenation in the presence of molecular oxygen.This molecular oxygen assisted ODH process relies on utilizing oxygen toextract H from an alkane, such as propane, to convert it to propyleneand have water and heat as by-products. Due to the electronegativitydifference, this reaction, shown in equation (2), theoretically occursat a lower temperature than PDH technology.

$\begin{matrix}{{{C_{3}H_{8}} + {0.5O_{2}}}\overset{Catalyst}{\rightarrow}{{C_{3}H_{6}} + {H_{2}O} + \Delta}} & (2)\end{matrix}$

However, using a strong oxidant, such as O₂, negatively affects theselectivity due to the formation of undesired products, such as CO andCO₂. As a result, a majority of the O₂—ODH catalysts fail to meet theperformance of PDH catalysts, where selectivity drops sharply with anincrease in propane conversion. As an alternative, sulfur or sulfurderivatives, such as H₂S, are used which resemble a softer oxidant.Transition state metal sulfide catalysts have been shown to be activetowards conversion of butane to iso-butene. These sulfide catalysts havea lower activation energy barrier for C—H activation than C—C bondactivation, making them much more effective than the PDH catalysts.However, as these catalysts react with the alkane, some sulfur is lostas H₂S, thus reducing the catalyst activity. Some sulfide catalysts havebeen reported for propane to propylene conversion which operate byco-feeding H₂S and H₂ with propane. However, these catalysts alsorequire a regeneration step with air followed by H₂S and H₂ mixture toregain the active metal sulfide catalyst.

A major drawback of the catalytic ODH system is that the oxidant streamand the alkane stream must be co-fed in the reactor. This results in theformation of undesired side products, which decrease the selectivity ofthe desired alkene. Also, in the case of sulfur, the metal sulfidecatalyst may lose its activity as the catalyst reduction reactionsdominate the catalyst oxidation reactions. This imbalance results in theuse of extreme catalyst regeneration steps, limiting the efficiency andturnover of the process.

SUMMARY

Generally, the instant disclosure relates to alkene generation usingmetal sulfide particles. In one aspect, a method can include providing agaseous alkane input stream to a first reactor and providing a metalsulfide (MS_(x)) particle to the first reactor, whereupon the metalsulfide (MS_(x)) particle reacts with an alkane in the gaseous alkaneinput stream to generate an alkene, a reduced metal sulfide (MS_(x-1))particle, and at least one of: hydrogen sulfide (H₂S) and a sulfurcontaining compound. The method can also include collecting a productstream from the first reactor including the alkene, hydrogen sulfide(H₂S) and/or the sulfur containing compound, providing the reduced metalsulfide (MS_(x-1)) particle to a second reactor, providing a sulfurstream to the second reactor, whereupon the reduced metal sulfide(MS_(x-1)) particle reacts with sulfur in the sulfur stream to generatethe metal sulfide (MS_(x)) particle and hydrogen (H₂). Then a secondreactor output stream including hydrogen (H₂) can be collected.

In another aspect, a method can include providing a gaseous alkane inputstream to a reactor, the reactor including a metal sulfide (MS_(x))particle, whereupon the metal sulfide (MS_(x)) particle reacts with analkane in the gaseous alkane input stream to generate an alkene, areduced metal sulfide (MS_(x-1)) particle, and at least one of: hydrogensulfide (H₂S) and one or more sulfur containing compounds selected from:S₂, CS, and CS₂. The method can also include collecting a product streamfrom the reactor including the alkene, hydrogen sulfide (H₂S) and/or theone or more sulfur containing compounds, after collecting the productstream, providing an inert gas stream to the reactor, after providingthe inert gas stream to the reactor, providing a sulfur stream to thereactor, whereupon the reduced metal sulfide (MS_(x-1)) particle reactswith sulfur in the sulfur stream to generate the metal sulfide (MS_(x))particle and hydrogen (H₂), and collecting a reactor output streamincluding hydrogen (H₂).

There is no specific requirement that a material, technique or methodrelating to alkene generation include all of the details characterizedherein, in order to obtain some benefit according to the presentdisclosure. Thus, the specific examples characterized herein are meantto be exemplary applications of the techniques described, andalternatives are possible.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing thermodynamic equilibrium for alkaneconversion to alkene via dehydrogenation.

FIG. 2 is a schematic diagram showing an exemplary two reactor systemfor generating alkenes.

FIG. 3 is a schematic diagram showing an exemplary single reactor systemfor generating alkenes.

FIG. 4 is a schematic diagram of an exemplary method for operating thetwo reactor system shown in FIG. 2.

FIG. 5 is a schematic diagram showing an exemplary method for operatingthe single reactor system shown in FIG. 3.

FIG. 6 is a graph showing experimental data for propane conversion andpropylene selectivity values over time for an oxidative dehydrogenationreaction including propane, H₂S, and Fe_(0.89)S at 650° C.

FIG. 7 is a graph showing experimental data for H₂S conversion over timefor the sulfidation reaction of FeS to form Fe_(0.89)S at 850° C.

FIG. 8 is a graph showing experimental data for temperature dependenceof iron vacancy in Fe—S system for a sulfidation reaction.

FIG. 9 is a graph showing experimental data for temperature dependenceof iron vacancy in Fe—S system for an oxidative dehydrogenationreaction, assuming H₂ to be the reactive species from alkanedehydrogenation.

FIG. 10 is a graph showing experimental data for propane conversion andpropylene selectivity values over time for an oxidative dehydrogenationreaction including propane, H₂S, and Fe_(0.89)S+SiO₂ at 600° C.

FIG. 11 is a graph showing experimental data for H₂S conversion overtime for the sulfidation reaction of FeS to form Fe_(0.89)S at 850° C.

FIG. 12 is a graph showing experimental data for moles of pyrite (FeS₂)and Fe₇S₈ at sulfur loadings greater than 1.

FIG. 13 is a graph showing experimental data for moles of pyrrhotitephase across temperatures 200-900° C. for sulfur loading less than 1.

FIG. 14 is a graph showing experimental data for moles of pyrrhotite andtrendlines for sulfur loadings 1-2 in the T350-650 zone.

FIG. 15 is a graph showing experimental data for moles of pyrite (FeS₂)and trendlines for sulfur loadings 1-2 in the T350-650 zone.

FIG. 16 is a graph showing experimental data for pyrrhotite sulfidationextent for sulfur loading 0-1 and 1-2 across temperatures 200° C.-900°C.

FIG. 17 is a graph showing experimental data for H₂S generation capacityfor different metal sulfides.

FIG. 18 is a graph showing experimental data for regenerability with H₂Sfor different metal sulfides.

FIG. 19 is a graph showing experimental data for H₂S generation capacityof a Co—S system for different temperatures.

FIG. 20 is a graph showing experimental data for H₂S generation capacityof a Pb—S system for different temperatures.

DETAILED DESCRIPTION

Systems and methods disclosed and contemplated herein relate to alkenegeneration. Disclosed systems and methods employ reducible metalsulfides during conversion of alkanes to alkenes, typically in achemical looping reactor system. Some implementations can utilize tworeactor systems. Some implementations can utilize single, fixed bedreactor systems.

In certain aspects, systems and methods disclosed herein address one ormore drawbacks of catalytic ODH reactions by splitting an oxidant streamand an alkane stream. In some instances, those streams are provided totwo reactors operating independent of each other. In some instances,those streams are sequentially provided to a single reactor. Generally,an alkane or a mixture of alkanes reacts with a metal sulfide (MS_(x))to form the alkene, H₂S and/or a sulfur containing compound in areactor. Here M is the metal component of the metal sulfide and Srepresents the sulfur in the solid lattice. Thus, the metal sulfide actsas the sulfur source that carries out the oxidation of H₂ to H₂S, thusimproving the alkane conversion.

During exemplary operation of a two reactor system, the MS_(x) canreduce to MS_(x-1), which is sent to the sulfidation reactor where asulfur source regenerates the metal sulfide into its original form, i.e.MS₂. This regeneration is different from the regeneration steps in acatalytic system, because this operation is a part of the chemicallooping structure. The regeneration step in a catalytic system iscarried out to address the loss of reactivity of the catalyst undernon-ideal and unstable conditions. However, an ideal catalyst wouldportray a stable performance, without requiring a regeneration step. Thechemical looping mode, however, intentionally carries out the reductionand oxidation reactions and the oxidation or regeneration reaction isperformed to complete the loop. In other words, the metal sulfide can beconsidered as a sulfur carrier between the two reactors, where the tworeactors follow very different reaction mechanisms. The regenerationreactor is also capable of producing a value-added product such as H₂,which is not the case in the catalytic system. The chemical looping modethus allows for the two reactors to be governed by differentthermodynamic and kinetic factors based on their operating parameters.

I. CHEMICAL ASPECTS

Systems and methods of the present disclosure may include input streamsprovided to reactor systems and output streams generated by reactorsystems. The sections below discuss various chemical aspects ofexemplary systems and methods.

A. Input Streams

Exemplary reactor systems may receive a gaseous alkane input stream anda sulfur stream. In two reactor configurations, exemplary reactors mayalso receive metal sulfide particles.

Gaseous alkane input streams may include one alkane species or may be amixture of alkane species. As implied, alkanes in gaseous alkane inputstreams are in a gaseous phase.

Alkanes usable in gaseous alkane input streams may be linear, branched,or cyclic. In some implementations, gaseous alkane input streams mayinclude at least one C₂-C₆ alkane. In some instances, gaseous alkaneinput streams may include only C₂ alkanes, only C₃ alkanes, only C₄alkanes, only C₅ alkanes, or only C₆ alkanes. In some instances, gaseousalkane input streams may include a mixture of C₂-C₅ alkanes; a mixtureof C₃-C₆ alkanes; a mixture of C₂-C₄ alkanes; a mixture of C₃-C₅alkanes; a mixture of C₄-C₆ alkanes; a mixture of C₂ and C₃ alkanes; amixture of C₃ and C₄ alkanes; a mixture of C₄ and C₅ alkanes; or amixture of C₅ and C₆ alkanes. Example alkanes may include, but are notlimited to, ethane, propane, n-butane, n-pentane, and n-hexane.

In some instances, gaseous alkane stream input may also contain CH₄ asan alkane component. CH₄ may or may not react with the metal sulfidedepending on the operating conditions.

In some instances, gaseous alkane input streams may also include one ormore non-alkane components, such as inert components. Example non-alkanecomponents that may be present in gaseous alkane input streams include,but are not limited to, hydrogen (H₂), nitrogen (N₂) and argon (Ar).

Example sulfur streams may include one or more allotropes of sulfur. Forinstance, exemplary sulfur streams may include, but are not limited to,S₂, S₃, S₄, and S₅. In some instances, example sulfur streams mayinclude hydrogen sulfide (H₂S) and/or mercaptans like CH₃SH. In someinstances, example sulfur streams may include one or more inert carriergases including, but not limited to, nitrogen (N₂) and argon (Ar).

In single reactor configurations, example reactors may also receiveinert gas streams. Example inert gas streams may include, but are notlimited to, nitrogen (N₂) and/or argon (Ar).

B. Output Streams

Exemplary reactor systems may generate various output streams. In tworeactor configurations, one reactor may provide an output streamincluding one or more desired products and the other reactor may providea second output stream.

Exemplary output streams may include one or more desired products. Forinstance, a metal sulfide (MS_(x)) particle reacting with an alkane inthe gaseous alkane input stream may generate an alkene, a reduced metalsulfide (MS_(x-1)), and one or more of: hydrogen sulfide (H₂S) and othersulfur containing products like S₂, among other products. In singlereactor and two reactor configurations, a product stream may include thegenerated alkene and one or more of hydrogen sulfide (H₂S) and othersulfur containing products, among other products. In two reactorconfigurations, the reduced metal sulfide (MS_(x-1)) may be provided tothe other reactor.

As another example, a reduced metal sulfide (MS_(x-1)) particle reactingwith sulfur in a sulfur stream may generate a metal sulfide (MS_(x))particle. In some instances, a reactor output stream can include thegenerated hydrogen (H₂) when the input sulfur stream to the reactorcontains a hydrogen feed such as H₂S. In some instances, a reactoroutput stream may include hydrogen sulfide (H₂S). In two reactorconfigurations, the metal sulfide (MS_(x)) particle may be provided tothe first reactor.

C. Reactions

Various reactions may occur in exemplary reactor systems. For example,alkane(s) and metal sulfide (MS_(x)) may be provided to a reactor. Themetal sulfide MS_(x) may be capable of donating its sulfur to H₂ to formH₂S and alkene(s). In this process, MS_(x) converts to MS_(x-1), whichmay be sent to a second reactor (or which may remain in the reactor insingle reactor configurations). An input stream that includes sulfur maybe used to regenerate the MS_(x-1) to MS_(x), where the MS_(x-1) reactswith sulfur in the input stream to form MS_(x).

Exemplary reactions are provided below without limitation. Inimplementations where propane is provided as an alkane, reaction (3) mayoccur in a reactor that includes a metal sulfide (MS_(x)) particle.

$\begin{matrix}\left. {{C_{3}H_{8}} + {MS_{x}}}\rightarrow{{C_{3}H_{6}} + {H_{2}S} + {MS_{x - 1}}} \right. & (3)\end{matrix}$

In implementations where a reactor includes a reduced metal sulfide(MS_(x-1)) particle and receives a sulfur stream that includes H₂S,reaction (4) may occur:

$\begin{matrix}\left. {{MS_{x - 1}} + {H_{2}S}}\rightarrow{H_{2} + {MS_{x}}} \right. & (4)\end{matrix}$

In implementations where butane is provided as an alkane, reaction (5)may occur in a reactor that includes a metal sulfide (MS_(x)) particle.

$\begin{matrix}\left. {{C_{4}H_{10}} + {MS_{x}}}\rightarrow{{C_{4}H_{8}} + {H_{2}S} + {MS_{x - 1}}} \right. & (5)\end{matrix}$

In implementations where a reactor includes a reduced metal sulfide(MS_(x-1)) particle and receives a sulfur stream that includes S₈,reaction (6) may occur:

$\begin{matrix}\left. {{MS_{x - 1}} + {\left( {1/8} \right)S_{8}}}\rightarrow{MS_{x}} \right. & (6)\end{matrix}$

D. Metal Sulfide Particles

Various types of metal sulfide particles may be utilized in exemplarysystems and methods. Generally, metal sulfide particles used inexemplary systems and methods are either in a reduced form or in anoxidized form. The reduced or oxidized terms refer to the change inoxidation state of the metal, lattice sulfur species, or both. Oxidizedmetal sulfide particles can react with an alkane, dehydrogenate thealkane, and form H₂S, which reduces the oxidized metal sulfide particleinto a reduced metal sulfide or a metal/metal alloy. The reduced metalsulfide particle or metal/metal alloy can accept sulfur in the solidlattice from a sulfur source. Upon sulfur addition/oxidation, reducedmetal sulfide particles can form oxidized metal sulfide particles.

Exemplary metal sulfide particles have an active metal capable offorming sulfides where active metal, sulfur, or both display one or morethan one oxidation states. Generally, example metals (M) may betransition state, metalloid, or rare earth metals. In some instances,example metal sulfide particles may be bimetallic or trimetallic.Example metals (M) include, but are not limited to, Fe, Co, Ni, Cu, W,La, Ce, Ti, Zn, Cd, Ru, Rh, and Pb. The metals may include sulfide(S²⁻), persulfide (S₂ ²⁻), or another sulfur species.

There may be more than one active metal in a metal sulfide either in theform of a mixed metal sulfide or as a promotor or dopant. Dopants andpromoters may be alkali metals, alkaline earth metals, transition statemetals, metalloid metals, or rare earth metals. Supports may be inertoxides of alkali metals, sulfides of alkali metals, alkaline earthmetals, transition state metals, metalloid metals, or rare earth metals.The amount of support, promotor, or dopant material may vary from 0.01wt %, 10 wt %, 20 wt %, 30 wt % 40 wt %, 50 wt %, 60 wt %, 70 wt %, 80wt %, 90 wt % or any value in between.

The metal sulfide may contain metal sulfides from group I or group II inthe form of promotor, dopant, or to form mixed metal sulfides. Inertsulfides such as, but not limited to MoS₂, Ce₂S₃, MgS, Na₂S may be usedas supports and dopants and promotors as well. Inert oxides that do notreact with the metal sulfide may be used as promotor, dopant, or as asupport. Examples of promotors, dopants, or supports may include, butnot limited to, K₂O, MgO, SiO₂, and Al₂O₃, as well as mixed metal oxidessuch as Mg Al₂O₄.

Oxides that do react with the sulfide to form metastable structures canalso be considered as a metal sulfide. Dopants, promotors, and supports,in addition to other components, may provide high surface area, highlyactive sulfur vacancies.

Exemplary metal sulfide particles may be synthesized by any suitablemethod including, but not limited to, wet milling, extrusion,pelletizing, freeze granulation, co-precipitation, wet-impregnation,sol-gel, and mechanical compression. Certain techniques may be used toincrease the strength and/or reactivity of exemplary metal sulfideparticles, such as sintering synthesized particles or adding a binder orsacrificial agent with synthesis methods such as sol-gel combustion.

Exemplary metal sulfide particles may be provided as powders or pellets.Example powders may include metal sulfide particles having a size ofabout 100 μm. Example pellets may include metal sulfide particles havinga size of about 2 mm.

Example metal sulfide particles may be bulk structures or mesoporoussupported nanoparticles. Example bulk structures may have randomorientations of large grains, cage-like structures for added physicalstrength, layered structure, or similar configurations. Examplemesoporous supported metal sulfide particles may have a mesoporoussupport such as Santa Barbara Amorphous-15 silica (SBA-15), SantaBarbara Amorphous-16 silica (SBA-16), and other SBA variants,Mesoporous-Al₂O₃, Mesoporous CeO₂, etc., which have micro and mesopores, in which metal sulfide nanoparticles may be embedded.

Example metal sulfide particles may have various densities. Forinstance, example metal sulfide particles may have a density of from 1.5g/cm³ to 6 g/cm³. In various implementations, example metal sulfideparticles may have a density of from 1.5 g/cm³ to 3 g/cm³; 3 g/cm³ to 6g/cm³; 2 g/cm³ to 4 g/cm³; 4 g/cm³ to 6 g/cm³; 1.5 g/cm³ to 2 g/cm³; 2g/cm³ to 3 g/cm³; 3 g/cm³ to 4 g/cm³; 4 g/cm³ to 5 g/cm³; or 5 g/cm³ to6 g/cm³.

II. REACTOR CONFIGURATIONS AND OPERATING CONDITIONS

Exemplary reactor systems may be single reactor system configurations ortwo reactor system configurations. In single reactor systemconfigurations, example reactors may be configured to be fixed bedreactors. In two reactor system configurations, example reactors may beconfigured to be moving beds, ebullated beds, fluidized beds, orcombinations thereof.

Exemplary reactor systems disclosed and characterized herein can operateunder temperatures and pressures sufficient for alkene generation andmetal sulfide regeneration.

Temperatures within exemplary reactors during oxidative dehydrogenation(performed in the first reactor in two reactor systems) are typicallybetween 200° C. and 1200° C. In various implementations, a temperatureof an exemplary reactor during oxidative dehydrogenation can be between300° C. to 1100° C.; 400° C. to 1000° C.; 200° C. to 500° C.; 500° C. to800° C.; 800° C. to 1100° C.; 400° C. to 800° C.; 800° C. to 1200° C.;500° C. to 700° C.; 700° C. to 900° C.; 900° C. to 1100° C.; 600° C. to800° C.; 400° C. to 500° C.; 500° C. to 600° C.; 600° C. to 700° C.;700° C. to 800° C.; 800° C. to 900° C.; or 900° C. to 1000° C.

Temperatures within exemplary reactors during sulfidation (performed inthe second reactor in two reactor systems) are typically between 200° C.and 1000° C. In various implementations, a temperature of an exemplaryreactor during sulfidation can be between 300° C. to 900° C.; 400° C. to800° C.; 200° C. to 600° C.; 600° C. to 1000° C.; 300° C. to 500° C.;500° C. to 700° C.; 700° C. to 925° C.; 300° C. to 400° C.; 400° C. to500° C.; 500° C. to 600° C.; 600° C. to 700° C.; 700° C. to 800° C.; or800° C. to 1000° C.

Pressures within exemplary reactors during oxidative dehydrogenation(performed in the first reactor in two reactor systems) are typicallybetween 1 atm and 30 atm. In various implementations, a pressure of anexemplary reactor during oxidative dehydrogenation can be between 1 atmand 15 atm; 15 atm and 30 atm; 2 atm and 25 atm; 5 atm and 20 atm; 1 atmand 5 atm; 5 atm and 10 atm; 10 atm and 15 atm; 15 atm and 20 atm; 20atm and 25 atm; 25 atm and 30 atm; 1 atm and 3 atm; 3 atm and 6 atm; 6atm and 9 atm; 9 atm and 12 atm; 1 atm and 2 atm; 2 atm and 3 atm; 3 atmand 4 atm; 4 atm and 5 atm; 5 atm and 6 atm; 6 atm and 7 atm; 7 atm and8 atm; 8 atm and 9 atm; or 9 atm and 10 atm.

Pressures within exemplary reactors during sulfidation (performed in thesecond reactor in two reactor systems) are typically between 1 atm and30 atm. In various implementations, a pressure of an exemplary reactorduring sulfidation can be between 1 atm and 15 atm; 15 atm and 30 atm; 2atm and 25 atm; 5 atm and 20 atm; 1 atm and 5 atm; 5 atm and 10 atm; 10atm and 15 atm; 15 atm and 20 atm; 20 atm and 25 atm; 25 atm and 30 atm;1 atm and 3 atm; 3 atm and 6 atm; 6 atm and 9 atm; 9 atm and 12 atm; 1atm and 2 atm; 2 atm and 3 atm; 3 atm and 4 atm; 4 atm and 5 atm; 5 atmand 6 atm; 6 atm and 7 atm; 7 atm and 8 atm; 8 atm and 9 atm; or 9 atmand 10 atm.

Various flow rates may be used within exemplary reactors duringoxidative dehydrogenation (performed in the first reactor in two reactorsystems) and sulfidation (performed in the second reactor in two reactorsystems). Specific flow rates can vary, particularly depending upon thescale of the operation, based on the stoichiometry and reaction kineticsof particular alkane and MS_(x) pairs or sulfur-containing MS pairs. Forillustration, example gas hourly space velocities can vary from 1ml/g·hr to 5000 ml/g·hr.

For the single reactor configuration, the temperature, pressure and gashourly space velocities mentioned for the two-reactor system areapplicable.

For the single reactor configuration, the outlet gas composition may bemeasured or estimated to determine the segment times of the alkanedehydrogenation step or the sulfidation step.

The threshold value for the alkane dehydrogenation step may bedetermined by the conversion of the alkane, selectivity of the desiredalkene, H₂S/Sulfur containing compounds produced or a combination ofthese parameters.

The threshold value for the inert purging step may be determined by thevolume of the reactor. The time for this segment can be determined bysending the inert gas into the reactor where the volume of the gasinside the reactor is replaced by anywhere between 2 to 10 times toensure the gas has been purged.

The threshold value for the sulfidation step is determined by the amountof sulfur that reacted with the reduced metal sulfide. This may beestimated by measuring the difference between the sulfur in the inletand outlet streams through gas analyzers.

III. SYSTEM ARRANGEMENTS

FIG. 2 shows a schematic diagram of an exemplary reactor system 100. Asshown, reactor system 100 includes reactor 102, reactor 104, alkanesource 106, and sulfur source 114. Reactor system 100 is an exampleembodiment of a two reactor system that may be used for alkenegeneration using metal sulfides. Reactor system 100 may be configuredfor continuous operation. Other embodiments may include more or fewercomponents.

Reactor 102 receives gaseous alkane input stream 108 and metal sulfide(MS_(x)) particles via input 118. The metal sulfide (MS_(x)) particlesreact with alkane from gaseous alkane input stream 108 to generate analkene, a reduced metal sulfide (MS_(x-1)) particle, hydrogen sulfide(H₂S) and other sulfur containing streams formed during the reaction.The reduced metal sulfide (MS_(x-1)) particles are provided to reactor104 via input 110.

Alkane source 106 provides one or more alkanes to reactor 102 in gaseousalkane input stream 108. Alkane source 106 may be configured to adjust aflow rate of gaseous alkane input stream 108. In some instances, theflow rate of gaseous alkane input stream 108 may be adjusted based onconversion data for an output stream 112 of reactor 102.

Reactor 102 provides a product stream 112 that includes alkene andhydrogen sulfide H₂S). Product stream 112 can also include one or moresulfur-containing compounds. In some instances, product stream 112includes one or more monitoring units to monitor conversion rates inreactor 102. Based on measured conversion rates, flow rates of thegaseous alkane input stream 108 and/or metal sulfide particles (MS_(x))may be adjusted to achieve desired conversion rates.

Reactor 104 may receive a sulfur stream 116 from sulfur source 114 andreduced metal sulfide (MS_(x-1)) particles 110 from reactor 110. Inreactor 104, the reduced metal sulfide (MS_(x-1)) particles may reactwith sulfur in the sulfur stream to generate the metal sulfide (MS_(x))particle and hydrogen (H₂). One or more additional components may begenerated depending upon constituents in sulfur stream 116.

Sulfur source 114 provides a sulfur stream 116 to reactor 104. Sulfursource 114 may be configured to adjust a flow rate of sulfur stream 116.In some instances, the flow rate of sulfur stream 116 may be adjustedbased on conversion data for an output stream 120 of reactor 104. Invarious implementations, and as discussed in greater detail above,sulfur stream 116 may include one or more allotrope of sulfur and/orhydrogen sulfide (H₂S).

Reactor 104 provides metal sulfide (MS_(x)) particles to reactor 102.Reactor 104 also provides an output stream 120 that includes one or moregaseous components. For instance, output stream 120 can include hydrogen(H₂).

Output stream 120 may include hydrogen sulfide (H₂S). In some instances,reactor system 100 may also include one or more separation units (notshown in FIG. 2) that can separate hydrogen sulfide (H₂S) from outputstream 120. Then, the separated hydrogen sulfide (H₂S) may be recycledto reactor 104.

In some instances, reactor system 100 may include one or more separationunits (not shown in FIG. 2) that can separate hydrogen sulfide (H₂S)from product stream 112 generated by reactor 102. Then, the separatedhydrogen sulfide (H₂S) may be recycled to reactor 104.

FIG. 3 shows a schematic diagram of example reactor system 200. Asshown, reactor system 200 includes reactor 208, alkane source 202, inertgas source 212, and sulfur source 218. Reactor system 200 is anexemplary embodiment of a single reactor system that may be used foralkene generation using metal sulfides. Reactor system 200 may beconfigured for batch operation. Other embodiments may include more orfewer components.

Alkane source 202 may provide a gaseous alkane input stream 204 toreactor 208. One or more flow regulation units 206 may be used toselectively provide gaseous alkane input stream 204 to reactor 208and/or control a flow rate of gaseous alkane input stream 204. Exemplarycomponents that may be included in gaseous alkane input stream 204 arediscussed in greater detail above.

Reactor 208 may be configured as a fixed bed reactor including metalsulfide (MS_(x)) particles. In reactor 208, the metal sulfide (MS_(x))particles may react with alkane in gaseous alkane input stream 204 togenerate an alkene, a reduced metal sulfide (MS_(x-1)) particle, andhydrogen sulfide (H₂S).

Reactor 208 may generate a product stream 224 that includes alkene andhydrogen sulfide (H₂S), and, in some instances, sulfur-containingcompounds. Gas analyzer unit 211 may monitor alkane conversion and/oralkene selectivity. One or both of those values can be compared to athreshold value and, upon reaching the value, flow regulation unit 206may stop the flow of gaseous alkane input stream 204 to reactor 208.

Inert gas source 212 may provide an inert gas stream 214 to reactor 208.One or more flow regulation units 216 may be used to selectively provideinert gas stream 214 to reactor 208 and/or control a flow rate of inertgas stream 214. Exemplary components of inert gas stream 214 arediscussed in greater detail above. Generally, inert gas stream 214 canpurge alkane(s), H₂S, and alkene gas from reactor 208.

Gas analyzer unit 211 may monitor alkane(s), H₂S, and alkene gas contentin output stream 224. Upon detecting that most or all of thosecomponents are not present in output stream 224, flow regulation unit216 may be configured to stop a flow of inert gas stream 214.

Sulfur source 218 may provide a sulfur stream 220 to reactor 208. One ormore flow regulation units 222 may be used to selectively provide sulfurstream 220 to reactor 208 and/or control a flow rate of sulfur stream220. Example components of sulfur stream 220 are discussed in greaterdetail above.

Gas analyzer unit 211 may be used to monitor hydrogen (H₂) content inoutput stream 224. Upon detecting a desired conversion of metal sulfide,flow regulation unit 222 may be configured to stop a flow of sulfurstream 220. Another purge of reactor 208 can be subsequently run byproviding the inert gas stream 214 to reactor 208.

Usually, reactor 208 receives only one of gaseous alkane input stream204, inert gas stream 214, and sulfur stream 220 at a time. That is,those streams are usually not mixed together and provided to reactor208.

IV. METHODS OF OPERATION

FIG. 4 shows example method 300 for operating a reactor system. In someinstances, method 300 may be used to operate example two reactor system100 discussed above with reference to FIG. 2. Other embodiments ofmethod 300 may include more or fewer operations.

Method 300 may begin by providing a gaseous alkane input stream(operation 302) to a first reactor. The alkane in the gaseous alkaneinput stream may include at least one C₂-C₆ alkane. Other aspects of thegaseous alkane input stream are discussed in greater detail above.

Metal sulfide (MS_(x)) particles also may be provided (operation 304) tothe first reactor. Various aspects of exemplary metal sulfide (MS_(x))particles are discussed in greater detail above. In the first reactor,the metal sulfide (MS_(x)) particles may react with alkane in thegaseous alkane input stream to generate an alkene, reduced metal sulfide(MS_(x-1)) particles, and hydrogen sulfide H₂S) and/or one or more othersulfur containing compounds.

In some instances, during operation, a temperature of the first reactormay be maintained to be between 200° C. and 1200° C. In some instances,during operation, a pressure of the first reactor may be maintained tobe between 1 atm and 30 atm.

During operation, a product stream may be collected (operation 306) fromthe first reactor. Typically, the product stream includes the alkenegenerated in the first reactor and hydrogen sulfide (H₂S). In someinstances, exemplary method 300 may also include separating the hydrogensulfide (H₂S) from the product stream and recycling the separatedhydrogen sulfide (H₂S) to the second reactor.

The reduced metal sulfide (MS_(x-1)) particles may be provided(operation 308) to the second reactor. A sulfur stream also may beprovided to the second reactor (operation 310). Various aspects ofexample sulfur streams, including example components, are discussedabove in greater detail. In the second reactor, the reduced metalsulfide (MS_(x-1)) particle reacts with sulfur in the sulfur stream togenerate the metal sulfide (MS_(x)) particle and hydrogen (H₂).

A second reactor output stream may be collected (operation 312). Thesecond reactor output stream may include, at least, hydrogen (H₂). Insome instances, the second reactor output stream may include hydrogensulfide (H₂S). Optionally, example method 300 may include separating thehydrogen sulfide (H₂S) from the second reactor output stream andrecycling the separated hydrogen sulfide (H₂S) to the second reactor.

FIG. 5 shows exemplary method 400 for operating a reactor system. Insome instances, method 400 can be used to operate a single reactorsystem 200 discussed above with reference to FIG. 3. Typically,exemplary method 400 is performed with a fixed bed reactor that includesmetal sulfide (MS_(x)) particles. Other embodiments of method 400 mayinclude more or fewer operations.

Method 400 may begin by providing a gaseous alkane input stream(operation 402) to the reactor. The alkane in the gaseous alkane inputstream may include at least one C₂-C₆ alkane. Other aspects of thegaseous alkane input stream are discussed in greater detail above. Themetal sulfide (MS_(x)) particles react with alkane in the gaseous alkaneinput stream to generate an alkene, a reduced metal sulfide (MS_(x-1))particle, and hydrogen sulfide (H₂S). A product stream is collected(operation 404) that includes, at least, the alkene and hydrogen sulfide(H₂S) and/or one or more other sulfur-containing compounds.

While providing the gaseous alkane input stream, the product stream canbe monitored for whether alkane conversion is below a predeterminedthreshold (operation 406). If alkane conversion is above thepredetermined threshold, the gaseous alkane input stream may becontinually provided (operation 402) to the reactor. In some instances,while providing the gaseous alkane input stream (operation 402), atemperature of the reactor may be maintained to be between 200° C. and1200° C. and a pressure of the reactor can be maintained to be between 1atm and 30 atm.

If alkane conversion is below the predetermined threshold, then thegaseous alkane input stream may be stopped, and an inert gas stream isprovided (operation 408) to the reactor. Providing the inert gas streamcan purge alkane, alkene, and H₂S from the reactor. In some instances, areactor output stream may be monitored, and inert gas may be provideduntil alkane, alkene, and/or H₂S content drops below a predeterminedthreshold. In some instances, the hydrogen sulfide (H₂S) may beseparated from the reactor output stream and recycled back to thereactor.

After providing the inert gas stream, a sulfur stream may be provided(operation 410) to the reactor. The sulfur stream may include one ormore sulfur-containing components, such as an allotrope of sulfur orhydrogen sulfide (H₂S). Additional details about the sulfur stream areprovided above. In some instances, while providing the sulfur stream(operation 410), a temperature of the reactor may be maintained to bebetween 200° C. and 1000° C. and a pressure of the reactor may bemaintained to be between 1 atm and 30 atm.

After providing the sulfur stream (operation 410), the reduced metalsulfide (MS_(x-1)) particle may react with sulfur in the sulfur streamto generate the metal sulfide (MS_(x)) particle and hydrogen (H₂). Thereactor output stream may be collected (operation 412), which includes,at least, hydrogen (H₂).

The reactor output stream may be monitored (operation 414) for whethermetal sulfide conversion in the reactor is above a predeterminedthreshold. If the metal sulfide conversion is below the predeterminedthreshold, the sulfur stream may be continued to be provided (operation410) to the reactor.

If the metal sulfide conversion is above the predetermined threshold,then sulfur stream may be stopped. Then, the inert gas stream may beprovided (operation 416) to the reactor. Providing the inert gas streamcan purge the reactor of gaseous species generated while sulfur wasprovided to the reactor. Then, method 400 may return to operation 402and gaseous alkane input stream can be provided to the reactor.

V. EXPERIMENTAL EXAMPLES

Experimental examples were conducted, and various aspects are discussedbelow. In particular, two experiments were conducted where metal sulfideparticles were iron (Fe)-based, propane was the alkane, and H₂S was thesulfur source.

A. Exemplary Fe—S System

An example first reactor was operated at 650° C. with a propane spacevelocity of 300 ml/g·hr and Fe_(0.89)S metal sulfide particles. Anexample second reactor was operated at 800° C. with an H₂S spacevelocity of 15 ml/g·hr. The reaction was carried out in a u-tube reactorand a mass spectrometer was used to measure the gas composition for thealkane dehydrogenation step. For the sulfidation step, a H₂S gasanalyzer was used. The mass spectrometer and the H₂S analyzer werecalibrated with known concentrations of gas mixtures. These continuousgas analyzers analyzed a slip stream of the product gas. Results forthis example system are shown in FIG. 6 and FIG. 7. FIG. 6 shows datafor the oxidative dehydrogenation reaction in the first reactor, andFIG. 7 shows an H₂S sulfidation reaction of FeS to Fe_(0.89)S.

A characteristic trend seen in FIG. 6 for propylene selectivity andpropane conversion can be attributed to the change in the surfacespecies with the reaction time. A maximum yield of propylene wascalculated to be 17.2%. A loss in sulfur from the iron sulfide in thefirst reactor is seen in the form of H₂S production in gas phase alongwith the propylene produced. The sulfidation reaction converts H₂S intoH₂, re-sulfating the iron sulfide into the original state of Fe_(0.89)S.

To measure the performance of metal sulfides, thermodynamic studies wereconducted using H₂ as reactant gas. There are two ways in which alkanescan interact with metal sulfides in S—ODH reactor, alkanes reactdirectly with metal sulfides to form alkenes and H₂S or alkanes canthermochemically crack over metal sulfide surface forming alkenes andH₂. This H₂ then reacts with metal sulfide to form H₂S. In both theseways, formation of H₂S drives the reaction and pushes dehydrogenationequilibrium forward. Hence, to assess metal sulfides for the proposedprocess, its ability to convert H₂ to H₂S should be measured as it isthe equilibrium determining reaction. In view of this, all thermodynamiccalculations on metal sulfides are performed with H₂ as reactant ratherthan any alkanes.

Generally, FIG. 8 and FIG. 9 show thermodynamic data for the Fe—Ssystem. FIG. 8 shows temperature dependence of iron (Fe) vacancy in theFe—S system for the sulfidation reaction. FIG. 9 shows temperaturedependence of iron (Fe) vacancy in the Fe—S system for the oxidativedehydrogenation reaction, assuming H₂ to be the reactive species fromalkane dehydrogenation. Under the current reaction conditions andtemperatures, the system favorably forms Fe_((1-x))S or pyrrhotitephase, where x varies between 0 and 0.2. The vacancy ‘x’ directlycorrelates to the amount of sulfidation of a particular phase.

B. Exemplary Fe—S—SiO₂ System

An example first reactor was operated at 600° C. with a propane spacevelocity of 60 ml/g·hr and Fe_(0.89)S+SiO₂ metal sulfide particles (SiO₂present in the particles at 20 wt %). An example second reactor wasoperated at 800° C. with an H₂S space velocity of 15 ml/g·hr. Theinstruments and methodology used are similar to Example A. Results forthis example system are shown in FIG. 10 and FIG. 11. FIG. 10 shows datafor the first reactor, and FIG. 11 shows an H₂S sulfidation reaction ofFeS to Fe_(0.89)S.

It appears that the added SiO₂, which played the role of a support,improved the surface area and the dispersion of active sites. The lowertemperature and lower space velocity in the first reactor (compared tothe experimental example above), appears to improve the overallselectivity and conversion of the system. The highest yield forpropylene with this system is 39%, which the sulfidation reactionshowing a similar trend as compared to the example above. The volcanotrend of the yield depicts a strong dependence of the performanceparameters with sulfur vacancies in the solid lattice. This providesinsight into a mechanism of the first reactor (where the oxidativedehydrogenation occurs), which can be leveraged to synthesize sulfidesthat yield higher propylene selectivity.

C. Exemplary Fe—S System at Various Conditions

Following the example depicted in FIG. 8 and FIG. 9, severalconfigurations of the MS_(x)-MS_(x-1) pair could be envisioned. In thisexample, thermodynamic studies using FactSage 7.3 were done on Fe—Ssystem to validate regenerability across a temperature range of 200°C.-1000° C. for both the reactors. 1 mol of Fe was sulfidized using 10mols of H₂S at a given temperature and the subsequent formed metalsulfide was reacted with 1 mol of H₂ to simulate system performance.Further, MS_(x) has been dubbed as FeS_(x) and MS_(x-1) has been dubbedas FeS_(y). In the following reactions (7)-(9), x is the sulfur presentin the most sulfidized metal phase, y is sulfur present in metal sulfidepost reaction with H₂, and m is the H₂S required to regenerate FeS_(y).

Reaction (7) shows a sulfidation step to set up the calculation.

$\begin{matrix}\left. {{Fe} + {10H_{2}S}}\rightarrow{{FeS}_{x} + {xH}_{2} + {\left( {{10} - x} \right)H_{2}S}} \right. & (7)\end{matrix}$

Reaction (8) shows a reaction of metal sulfide with H₂ (S—ODH).

$\begin{matrix}\left. {{FeS}_{x} + H_{2}}\rightarrow{{FeS}_{y} + {\left( {x - y} \right)H_{2}S} + {\left( {1 - \left( {x - y} \right)} \right)H_{2}}} \right. & (8)\end{matrix}$

The reduced metal sulfide was reacted with H₂S in incremental steps tillit was completely regenerated, as shown in reaction (9).

$\begin{matrix}\left. {{FeS}_{y} + {{mH}_{2}S}}\rightarrow{{FeS}_{x} + {\left( {x - y} \right)H_{2}} + {\left( {m - \left( {x - y} \right)} \right)H_{2}S}} \right. & (9)\end{matrix}$

The results for this example are given below in table 1.

TABLE 1 Regenerability of Fe—S System Amount of S remaining in Initialamount of sulfide post S in sulfide reaction with H₂ Amount of S toAmount of H₂S (mol of S/mol of (mol of S/mol of be regenerated required(mol of Temperature Fe) Fe) (mol of S/mol of H₂S/mol of Fe) (° C.) [x][y] Fe) [m] 200 2 1.901 0.099 0.11 300 2 1.454 0.546 1.2 400 2 1.1280.872 7.4 500 1.4 1.073 0.327 9 600 1.167 1.050 0.117 6 700 1.149 1.0410.108 3.5 800 1.131 1.033 0.098 3.5 900 1.114 1.026 0.088 2 1000 1.0981.021 0.077 1.5

In this experiment, it was observed that in the temperature range of200° C.-1000° C., iron metal sulfides swing between three phases: FeS₂,Fe₇S₈ and FeS_(z)(pyrrhotite z=1-1.25). Fe₇S₈ is not formed at 400° C.and above and FeS₂ is not formed at 600° C. and beyond. [x] and [y]values are calculated based on these phases. At lower temperatures of200° C. and 300° C., metal sulfide swings only between FeS₂ and Fe₇S₈.As the temperature reaches 400° C. metal sulfide swings between FeS₂ andFeS_(z). At 500° C., Fe is no longer sulfidized completely to FeS₂, andswing occurs between mixture of FeS₂ and FeS_(z) and pure FeS_(z).Beyond 500° C., swing occurs only in pyrrhotite phase with change in [z]value, for instance at 600° C. [z] value changes from 1.167 to 1.1050 asindicated from [x] and [y] values in Table 1.

It appears from Table 1 that regenerability is achieved for entiretemperature spectrum under different x and y values. Regenerationrequires high partial pressure of H₂S and hence, higher amount of H₂S isneeded even if all of it does not get converted.

D. Exemplary Fe—S System with S as the Sulfur in the Sulfur Stream

In all the following experimental examples, the iron loading was keptconstant at 1 mole and sulfur was used as the sulfur stream. Thetemperatures studied were divided into three zones based on theformation of iron sulfide phases. The temperature zones are 200-300° C.,300-650° C. and 650-900° C. In all the temperature zones, sulfur loadingwas varied to understand the product distribution and sulfidationextent.

1. Zone 200° C.-300° C. (T200-300)

In this temperature zone, when the sulfur loading is less than 1, it wasobserved that the product consists predominantly of the pyrrhotitephase. As the temperature was increased, the pyrrhotite phase decreased(FIG. 12) at a fixed sulfur loading. At these low loadings, there was nounreacted sulfur left in the solution (S-MATT) phase since it was thelimiting reactant. Limiting reactant is defined with respect to a moleof stoichiometric pyrrhotite (FeS).

Upon increasing the sulfur loading beyond 1 until 2, it was observedthat the pyrrhotite phase decomposed completely into two phases ofconstant molar quantities of pyrite (FeS₂) and Fe₇S₈ without anyunreacted sulfur across the entire temperature range. However, it isworth noting that with an increased sulfur loading (from 1 towards 2),the molar quantities of pyrite increased and pyrrhotite decreased acrossthe entire temperature range as illustrated in FIG. 12. This suggests ahigher sulfide product (pyrite) is favored over Fe₇S₈ on increasingtemperature when the sulfur is in excess with respect to iron.

Upon further increasing the sulfur loading beyond 2, it was observed thepyrrhotite fully decomposed into pyrite and the excess unreacted sulfurwas left in the solution (MATT) phase. There was also no formation ofpyrrhotite or Fe₇S₈ phase at these sulfur loadings. The trend isconsistent across the entire temperature range.

2. Zone 350° C.-650° C. (T350-650)

In this temperature zone, when the sulfur loading is less than 1, thetrends are similar to the T200-300 zone's sulfur loading <1. The productconsisted of only pyrrhotite which decreased as the temperature isincreased from 350° C. to 650° C. illustrated in FIG. 13.

When the sulfur loading is increased beyond 1 till 2, the productconsisted of two phases here i.e. pyrrhotite and pyrite (FeS₂). There isno formation of Fe₇S₈ in this zone unlike previous case. The molarquantities of pyrrhotite increased while the pyrite decreased asillustrated in FIG. 14 which is attributed to the pyrite decompositioninto pyrrhotite phase upon increasing the temperature. It is worthnoting that in this temperature zone, for the sulfur loadings of 1 to1.5 the dominant phase is pyrrhotite while from 1.5 to 2 it is pyrite asshown in FIG. 14. In addition, the pyrite decreases and pyrrhotiteincreases for sulfur loadings (1-2) with increase in temperature. Thisis illustrated through the trendlines in the FIG. 15.

For sulfur loadings beyond 2, no pyrrhotite is observed furthermoreacross the entire zone. The products obtained at excessive sulfur is amole of pyrite and the excess unreacted sulfur in found in the solution(S-MATT) phase till 450° C. While beyond 450° C. the unreacted sulfur ispresent in the gas phase in the form of S₂ since the temperature is wellbeyond the boiling point of sulfur.

3. Zone 700° C.-900° C. (T700-900)

In this temperature zone, the only phase is pyrrhottite across allranges of sulfur loading. Herein too the pyrrhottite phase decreasedwith increasing the temperature up until sulfur loading equals 1. Forsulfur loadings beyond 1, the product consists of 1 mole of pyrrhotiteand the excess unreacted sulfur is found in the gaseous phase in form ofS₂.

4. Zone 950° C.-1000° C. (T950-1000)

In this temperature range, to avoid the MATT phase, the sulfur loadingwas kept at excess with respect to iron (>1). The pyrrhotite phase wasformed and any unreacted sulfur was found in the gas phase in form ofS₂.

5. Extent of Sulfidation

The sulfidation extent is measured in the pyrrhotite phase across theentire temperature range (200° C.-900° C.). It was observed that thesulfidation increased with an increase of the temperature for sulfurloadings up till 1 while the sulfidation extent is peaked at 700° C. forsulfur loadings beyond 1. This is shown in FIG. 16.

E. Experimental Example with Mixed Metal Sulfides

In this example, thermodynamic analysis using FactSage 7.3 was done onFe—Ni—S and Fe—Cu—S system to determine improvement over Fe—S system. 1mol of Fe along with 1 mol of Ni/Cu was sulfidized using 10 mols of H₂Sat 600° C. The formed bimetallic sulfide was reacted with 1 mol of H₂ at600° C. The reactions were similar to those given in Fe—S section.Comparison based on H₂S generation for different metal sulfides isdepicted in FIG. 17. H₂S generation is normalized with respect to sulfurpresent in metal sulfide.

Fe—Cu—S system shows a 53% improvement in H₂S formation over an Fe—Ssystem. This means that Fe—Cu—S can push the equilibrium of alkanedehydrogenation using less amount of material. To confirm theregenerability of these bimetallic sulfides, sulfides post H₂ reactionwere reacted with incremental amounts of H₂S. As an amount of Fe remainsconstant, H₂S addition and sulfur content was normalized based on Fe tokeep consistent with Fe—S single sulfide system. Both the Fe—Cu—S andFe—Ni—S sulfides show complete regenerability at 600° C. as indicated byFIG. 18.

Like the pyrrhotite phase of Fe, bimetallic sulfides form phase of FeMSzwhere M is either Cu or Ni. The swing occurs between different [z]values. The change of [z] value for each sulfide can be calculated fromFIG. 18 by subtracting sulfur content at zero addition of H₂S withconstant sulfur content achieved after addition of enough H₂S.

F. Experimental Example with Co—S System

Metals other than Fe can exhibit multiple sulfidation states which canbe exploited for alkane dehydrogenation. In this example, thermodynamicstudy on another transition metal Co is performed to estimate itsoverall performance. Co cannot be sulfidized with H₂S, but it reactswith pure sulfur to form sulfides. 1 mol of Co was reacted with 10 molsof S at various temperatures. At every temperature, CoS₂ was obtained asthe most sulfidized phase which was reacted with 1 mol of H₂. Based onthe temperature, mixture of CoS and CoS₂ is obtained with generation ofH₂S and S.

Reaction (10) below shows sulfidation.

$\begin{matrix}\left. {{Co} + {10S}}\rightarrow{{CoS}_{2} + {8S}} \right. & (10)\end{matrix}$

Reaction (11) below shows reaction with H₂.

$\begin{matrix}\left. {{CoS}_{2} + H_{2}}\rightarrow{{a{CoS}} + {\left( {1 - a} \right){Co}S_{2}} + {{bH}_{2}S} + {\left( {1 - a - b} \right)S}} \right. & (11)\end{matrix}$

Results for H₂S and S generation are shown in FIG. 19. At lowtemperatures, entire conversion of CoS₂ is not obtained which results inpoor H₂S generation. Sulfur is also emitted in very low quantities at700° C. and 800° C.

At 600° C., Co—S system is better than Fe—S system by a factor of 3.76.This huge enhancement is possible because CoS₂ is very easily reduced toCoS by H₂. CoS can be regenerated back to CoS₂ using sulfur fortemperature range of 200° C.-800° C. as shown in Table 2.

TABLE 2 Regenerability of Co—S System Amount of S remaining in Initialamount of sulfide post S in sulfide reaction with H₂ Amount of S toAmount of S (mol of S/mol of (mol of S/mol of be regenerated required(mol of Temperature Co) Co) (mol of S/mol of S/mol of Co) (° C.) [x] [y]Co) [m] 200 2 1.612 0.388 0.388 300 2 1.266 0.734 0.734 400 2 1.1180.882 0.882 500 2 1.062 0.938 0.938 600 2 1.031 0.969 0.969 700 2 1 1 1800 2 1 1.1 1.1

As CoS₂ is always achieved as the most sulfidized phase, [x] value isalways 2. [y] value is calculated based on amount of CoS and CoS₂present, shown below:

[y] = mols  of  CoS + 2 * mols  of  CoS₂

As stated above, the table clearly shows low sulfide conversion at lowertemperatures. In contrast to Fe—S system, excess amount of sulfidizingagent (S) is not required to fully regenerate the sulfide.

G. Experimental Example with Pb—S System

Similar to transition metals, even metalloids such as Pb can displaymultiple oxidation states. Using H₂S, Pb can be sulfidized only untilPbS. PbS is a stable phase and does not react with H₂ in temperaturerange of 200° C.-700° C. and shows little reactivity at temperaturesabove 700° C. Hence, to achieve greater sulfidation, S is used tosulfidize and regenerate Pb metal sulfide. 1 mol of Pb was reacted with10 mols of S at various temperatures. A mixture of PbS and PbSz (z>1) isobtained which is then further reacted with 1 mol of H₂. The reactionscheme is similar to Co. The result for H₂S formation is depicted inFIG. 20.

The sulfided form of Pb tends to lose a lot of sulfur. However, as theanalysis was restricted to 1 mol of H₂, entire potential of this metalsulfide is not captured in the above figure. Above 800° C., some Pbevaporates in form of PbS and hence temperatures only up till 700° C.are considered. PbS phase is formed only till temperatures below 400° C.while PbSz is formed in entire temperature range. The reduced metalsulfide can be regenerated using stoichiometric amount of S as seen inTable 3.

TABLE 3 Regenerability of Pb—S System Amount of S remaining in Initialamount of sulfide post S in sulfide reaction with H₂ Amount of S toAmount of S (mol of S/mol of (mol of S/mol of be regenerated required(mol of Temperature Pb) Pb) (mol of S/mol of S/mol of Pb) (° C.) [x] [y]Pb) [m] 200 10 8.981 1.019 1.019 300 10 8.819 1.181 1.181 400 10 8.0841.916 1.916 500 10 6.146 3.854 3.854 600 5.292 2.656 2.636 2.636 7002.792 1 1.792 1.792

The tendency of Pb to retain S decreases as temperature increases and asalmost complete conversion of H₂ to H₂S is obtained, the H₂S produced/Sinput parameter increases with temperature as seen in FIG. 20. However,as mentioned earlier, metal sulfides at lower temperatures are capableof processing more H₂, which is not studied to keep the study consistentwith other metal systems. This can be seen by the difference in sulfurcontent between initial and reduced sulfided form (amount to beregenerated) which is being emitted as pure sulfur in this experimentalexample.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. In case of conflict, the present document, includingdefinitions, will control. Example methods and materials are describedbelow, although methods and materials similar or equivalent to thosedescribed herein can be used in practice or testing of the presentdisclosure. The materials, methods, and examples disclosed herein areillustrative only and not intended to be limiting.

The terms “comprise(s),” “include(s),” “having,” “has,” “can,”“contain(s),” and variants thereof, as used herein, are intended to beopen-ended transitional phrases, terms, or words that do not precludethe possibility of additional acts or structures. The singular forms“a,” “an” and “the” include plural references unless the context clearlydictates otherwise. The present disclosure also contemplates otherembodiments “comprising,” “consisting of” and “consisting essentiallyof,” the embodiments or elements presented herein, whether explicitlyset forth or not.

The modifier “about” used in connection with a quantity is inclusive ofthe stated value and has the meaning dictated by the context (forexample, it includes at least the degree of error associated with themeasurement of the particular quantity). The modifier “about” shouldalso be considered as disclosing the range defined by the absolutevalues of the two endpoints. For example, the expression “from about 2to about 4” also discloses the range “from 2 to 4.” The term “about” mayrefer to plus or minus 10% of the indicated number. For example, “about10%” may indicate a range of 9% to 11%, and “about 1” may mean from0.9-1.1. Other meanings of “about” may be apparent from the context,such as rounding off, so, for example “about 1” may also mean from 0.5to 1.4.

Definitions of specific functional groups and chemical terms aredescribed in more detail below. For purposes of this disclosure, thechemical elements are identified in accordance with the Periodic Tableof the Elements, CAS version, Handbook of Chemistry and Physics, 75^(th)Ed., inside cover, and specific functional groups are generally definedas described therein.

For the recitation of numeric ranges herein, each intervening numberthere between with the same degree of precision is explicitlycontemplated. For example, for the range of 6-9, the numbers 7 and 8 arecontemplated in addition to 6 and 9, and for the range 6.0-7.0, thenumber 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 areexplicitly contemplated. For example, when a pressure range is describedas being between ambient pressure and another pressure, a pressure thatis ambient pressure is expressly contemplated.

We claim:
 1. A method, comprising: providing a gaseous alkane inputstream to a first reactor; providing a metal sulfide (MS_(x)) particleto the first reactor, whereupon the metal sulfide (MS_(x)) particlereacts with an alkane in the gaseous alkane input stream to generate analkene, a reduced metal sulfide (MS_(x-1)) particle, and at least oneof: hydrogen sulfide (H₂S) and a sulfur containing compound; collectinga product stream from the first reactor including the alkene, hydrogensulfide (H₂S) and the sulfur containing compound; providing the reducedmetal sulfide (MS_(x-1)) particle to a second reactor; providing asulfur stream to the second reactor, whereupon the reduced metal sulfide(MS_(x-1)) particle reacts with sulfur in the sulfur stream to generatethe metal sulfide (MS_(x)) particle and hydrogen (H₂); and collecting asecond reactor output stream including hydrogen (H₂).
 2. The methodaccording to claim 1, wherein the alkane in the gaseous alkane inputstream includes at least one C₂-C₆ alkane; and wherein the sulfurcontaining compound is one or more of: S₂, CS, and CS₂.
 3. The methodaccording to claim 1, further comprising: monitoring alkane content inthe product stream; and if the alkane content differs from apredetermined target, adjusting a flow rate of the gaseous alkane inputstream.
 4. The method according to claim 1, wherein the sulfur streamincludes hydrogen sulfide (H₂S).
 5. The method according to claim 4,wherein the second reactor output stream further comprises hydrogensulfide (H₂S), the method further comprising: separating the hydrogensulfide (H₂S) from the second reactor output stream; and recycling theseparated hydrogen sulfide (H₂S) to the second reactor.
 6. The methodaccording to claim 1, wherein the sulfur stream includes at least oneallotrope of sulfur (S).
 7. The method according to claim 1, furthercomprising separating the hydrogen sulfide (H₂S) from the productstream; and recycling the separated hydrogen sulfide (H₂S) to the secondreactor.
 8. The method according to claim 1, further comprising:maintaining a temperature of the first reactor to be between 200° C. and1200° C.; maintaining a pressure of the first reactor to be between 1atm and 30 atm; maintaining a temperature of the second reactor to bebetween 200° C. and 1000° C.; and maintaining a pressure of the secondreactor to be between 1 atm and 30 atm.
 9. The method according to claim1, wherein the sulfur stream further includes an inert carrier gas. 10.The method according to claim 1, wherein a metal (M) in the metalsulfide (MS_(x)) particle includes iron (Fe), cobalt (Co), nickel (Ni),copper (Cu), tungsten (W), lanthanum (La), cerium (Ce), titanium (Ti),zinc (Zn), cadmium (Cd), ruthenium (Ru), rhodium (Rh) or lead (Pb). 11.The method according to claim 1, wherein the metal sulfide (MS_(x))particle includes a promotor, dopant, or support.
 12. The methodaccording to claim 11, wherein the promotor, dopant, or support is MoS₂,Ce₂S₃, MgS, Na₂S, K₂O, MgO, SiO₂, Al₂O₃, or MgAl₂O₄.
 13. The methodaccording to claim 1, wherein the metal sulfide (MS_(x)) particle has asize of 100 μm to 2 mm; and wherein the metal sulfide (MS_(x)) particlehas density of 1.5 g/cm³ to 6 g/cm³.
 14. The method according to claim1, wherein the metal sulfide (MS_(x)) particle includes a mesoporoussupport selected from: Santa Barbara Amorphous-15 silica (SBA-15), SantaBarbara Amorphous-16 silica (SBA-16), Mesoporous Al₂O₃, and MesoporousCeO₂.
 15. A method, comprising: providing a gaseous alkane input streamto a reactor, the reactor including a metal sulfide (MS_(x)) particle,whereupon the metal sulfide (MS_(x)) particle reacts with an alkane inthe gaseous alkane input stream to generate an alkene, a reduced metalsulfide (MS_(x-1)) particle, and at least one of: hydrogen sulfide (H₂S)and at least one sulfur containing compound, the at least one sulfurcontaining compound being selected from: S₂, CS, and CS₂; collecting aproduct stream from the reactor including the alkene and at least one ofhydrogen sulfide (H₂S) and the at least one sulfur containing compound;after collecting the product stream, providing an inert gas stream tothe reactor; after providing the inert gas stream to the reactor,providing a sulfur stream to the reactor, whereupon the reduced metalsulfide (MS_(x-1)) particle reacts with sulfur in the sulfur stream togenerate the metal sulfide (MS_(x)) particle and hydrogen (H₂); andcollecting a reactor output stream including hydrogen (H₂).
 16. Themethod according to claim 15, further comprising: after collecting thereactor output stream, providing the inert gas stream to the reactor,wherein the alkane in the gaseous alkane input stream includes at leastone C₂-C₆ alkane; and wherein the sulfur stream includes hydrogensulfide (H₂S).
 17. The method according to claim 15, wherein the sulfurstream includes at least one allotrope of sulfur (S); and wherein thereactor output stream includes hydrogen sulfide (H₂S), the methodfurther comprising: separating the hydrogen sulfide (H₂S) from thereactor output stream; and recycling the separated hydrogen sulfide(H₂S) to the reactor.
 18. The method according to claim 15, furthercomprising: while providing the gaseous alkane input stream: maintaininga temperature of the reactor to be between 200° C. and 1200° C.;maintaining a pressure of the reactor to be between 1 atm and 30 atm;while providing the sulfur stream: maintaining a temperature of thereactor to be between 200° C. and 1000° C.; and maintaining a pressureof the reactor to be between 1 atm and 30 atm.
 19. The method accordingto claim 15, wherein a metal (M) in the metal sulfide (MS_(x)) particleincludes iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), tungsten (W),lanthanum (La), cerium (Ce), titanium (Ti), zinc (Zn), cadmium (Cd),ruthenium (Ru), rhodium (Rh), or lead (Pb); and wherein the metalsulfide (MS_(x)) particle includes a promotor, dopant, or supportselected from MoS₂, Ce₂S₃, MgS, Na₂S, K₂O, MgO, SiO₂, Al₂O₃, or MgAl₂O₄.20. The method according to claim 15, wherein the metal sulfide (MS_(x))particle has a size of 100 μm to 2 mm; wherein the metal sulfide(MS_(x)) particle has density of 1.5 g/cm³ to 6 g/cm³; and wherein themetal sulfide (MS_(x)) particle includes a mesoporous support selectedfrom: Santa Barbara Amorphous-15 silica (SBA-15), Santa BarbaraAmorphous-16 silica (SBA-16), Mesoporous Al₂O₃, and Mesoporous CeO₂.